CN102367364A - Compound for producing a scratch-proof coating with improved lye resistance - Google Patents
Compound for producing a scratch-proof coating with improved lye resistance Download PDFInfo
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- CN102367364A CN102367364A CN201110124841XA CN201110124841A CN102367364A CN 102367364 A CN102367364 A CN 102367364A CN 201110124841X A CN201110124841X A CN 201110124841XA CN 201110124841 A CN201110124841 A CN 201110124841A CN 102367364 A CN102367364 A CN 102367364A
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- aryl
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- G02B1/105—
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
Abstract
Composition comprises: (a) a silane derivative of formula R 3>O-Si(OR 2>)(OR 4>)-OR 1>) (I) and/or hydrolysis- or condensation product of (I); (b) a silane derivative of formula (R 6>(R 7>) 3 - nSi(OR 5>) n) (II) and/or hydrolysis- or condensation products of (II); (c) a colloidal inorganic oxide, fluoride or oxyfluoride; (d) a cycloaliphatic or aromatic epoxide compound comprising at least two epoxide groups; and (e) a solvent comprising an alcohol, ether and/or ester. R 1>-R 5>alkyl, acyl, alkyleneacyl, cycloalkyl, aryl or alkylenearyl (all optionally substituted); R 6>organic residue comprising epoxide; R 7>optionally substituted alkyl, cycloalkyl, aryl or alkylenearyl; and n : 2 or 3.
Description
Technical field
The present invention relates to a kind of compsn that is used to make with the alkali-proof anti-resitant coatings of improvement.
Background technology
Transparent polymer is used in optics and the photoelectric field just day by day, and this is because these materials have advantage aspect loss of weight and the anti-fracture.In the precision optics field, have the assembly of more complicated three-dimensional geometrical structure, such as lens and lens element, also can be made with relatively large amount.
The exemplary plastic material that is used to optical field at present comprises polymethylmethacrylate, polycarbonate, diethylene glycol diene propylene carbonate (trade name
) and based on the specific high refrangibility polymkeric substance of polythiourethane.
One of shortcoming of these plastic materials is their low relatively surface hardness and scratch resistances.
The well-known method that is used to improve scratch resistance comprises that applying surface coating is as the sol-gel technology part., can use tetraalkoxysilane here, it can be in hydrolysis under the appropriate condition, and in case the silanol group generation condensation that produces through hydrolysis, tetraalkoxysilane will form the three-dimensional network silicate sturcture so.
Except having the highest possible scratch resistance, top coat also should satisfy other a series of requirements.These requirements be included in heat expose have minimum possible cracking down, strong as far as possible to the cohesiveness of substrate surface and strong as far as possible acid resistance and/or alkali resistance.In addition, the specific refractory power of coating should be able to be as much as possible adapts with the specific refractory power of base material.
Yet, when satisfying these standards, must consider the often conflict mutually each other of these performances, this makes that the raising of a performance can only be a cost to sacrifice another performance usually.
In order to improve the snappiness of silicate network; Expose rimose trend down thereby reduce it in heat, tetraalkoxysilane makes up use with organoalkoxysilane (for example remove alkoxyl group and have the silane of organic residue of one or more and Si atom Direct Bonding) usually.Though the organic and inorganic network structure that makes has bigger snappiness and alkaline stability, for pure inorganic silicate structure, this is that cost realizes to reduce hardness.
U.S. Pat 3,986,997 have described a kind of colloidal state SiO that comprises
2, and the aqueous compsn of the product that produces through hydrolysis and/or condensation such as methyltrimethoxy silane and/or this organotrialkoxysilane of organotrialkoxysilane.
Also known to tetraalkoxysilane or colloidal state SiO
2, with and organoalkoxysilane and the dicarboxylicacid or the dicarboxylic anhydride combination that comprise epoxy group(ing) of organic residue use.
U.S. Pat 2001/0049023 A1 discloses a kind of based on the compsn that comes coated substrate through the blended water-containing organic solvent, and it comprises (i) and has the organoalkoxysilane of epoxide function or the product of this organoalkoxysilane hydrolysis and/or condensation generation; The (ii) product of tetraalkoxysilane or this tetraalkoxysilane hydrolysis and/or condensation generation and (iii) dicarboxylicacid or dicarboxylic anhydride.
Tetraalkoxysilane/colloidal state SiO
2, with and the combination that comprises organoalkoxysilane and the dicarboxylicacid or the dicarboxylic anhydride of epoxy group(ing) of organic residue use also in U.S. Pat 4,355,135 with US 5,322,888 in come into question.
WO 2008/087741 discloses a kind of coating composition; It comprises: what (A) have aliphatic residue R1 gathers (methyl) glycidyl ether compound; (B) silicious sesquioxane, (C) alkoxy compound, (D) organic alkoxy compound; Wherein the organic residue with the Si atomic linkage has the cationic polymerizable group such as epoxy group(ing), and (E) photopolymerizable catalyzer.As for the suitable multi-functional epoxy compound as component (A), WO 2008/087741 is described to cyclic epoxy compound and is not suitable for the sufficiently rigid coating of manufacturing such as cyclic aliphatic and aromatic ring oxygen compound.
Summary of the invention
Consider above-mentioned information; The object of the present invention is to provide and a kind ofly can be created in the compsn that has the coating of better balance on the following performance: higher scratch resistance has low cracking trend simultaneously under heat exposes; Preferably to the cohesiveness of substrate surface, and higher acid resistance and/or alkali resistance.
The object of the invention is implemented through a kind of compsn of making coating that is applicable to is provided, and said composition comprises:
(a) hydrolysate and/or the condensation product of the silane derivative shown in silane derivative shown in the formula (I) and/or the formula (I),
R wherein
1, R
2, R
3And R
4Can be identical or different, they are selected from optionally can substituted alkyl, acyl group, alkylidene group acyl group, naphthenic base, aryl or alkylidene aryl,
(b) hydrolysate and/or the condensation product of the silane derivative shown in silane derivative shown in the formula (II) and/or the formula (II),
R
6R
7 3-nSi(OR
5)
n (II)
Wherein
-R
5Be without substituted or through substituted alkyl, acyl group, alkylidene group acyl group, naphthenic base, aryl or alkylidene aryl,
-R
6Be the organic residue that comprises epoxy group(ing),
-R
7Be without substituted or through substituted alkyl, naphthenic base, aryl or alkylidene aryl,
-n is 2 or 3,
(c) colloidal inorganic oxide, fluorochemical or oxyfluoride,
(d) have the cyclic aliphatic or the aromatic ring oxygen compound of at least two epoxy group(ing),
(e) comprise the solvent of alcohol, ether and/or ester.
Specifically said as follows, use the compsn comprise component (a) to (e) to produce to have height scratch resistance, higher alkali resistance, the coating of cohesive strength and lower cracking trend preferably.
Embodiment
As stated, compsn according to the present invention comprise silane derivative shown in the formula (I) and/or said silane derivative hydrolysate and/or condensation product as component (a).
Term " hydrolysate and/or the condensation product of the silane derivative shown in the formula (I) " shows; As part of the present invention; Hydrolysis can also take place through forming silanol group in silane derivative (I) at least in part, and to a certain degree crosslinked can take place in the condensation reaction of these silanol groups.
If R
1, R
2, R
3And/or R
4Be alkyl, be preferably C so
1-8Alkyl, or further be preferably C
1-4Alkyl, they still can optionally be substituted.For example, can use methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, hexyl or octyl group herein.
If R
1, R
2, R
3And/or R
4Be acyl group, it is preferably ethanoyl, propionyl group or butyryl radicals so.
If R
1, R
2, R
3And/or R
4Be the alkylidene group acyl group, it is preferably C so
1-6The alkylidene group acyl group (for example-CH
2-acyl group;-CH
2-CH
2-acyl groups etc.), wherein the acyl group unit is preferably ethanoyl, propionyl group or butyryl radicals.
Alkylidene group be understood that be divalent alkyl (for example-CH
2-;-CH
2-CH
2-etc.).
If R
1, R
2, R
3And/or R
4Be naphthenic base, so its be preferably optionally can substituted cyclohexyl residue.
If R
1, R
2, R
3And/or R
4Be aryl, so its be preferably optionally can substituted phenyl residues.
If R
1, R
2, R
3And/or R
4Be alkylidene aryl, so its be preferably optionally can substituted C
1-6The alkylidene aryl residue (for example-CH
2-aryl;-CH
2-CH
2-aryl etc.), wherein aryl unit is preferably phenyl.
Silane derivative shown in the preferred formula (I) comprises tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, tetraisobutoxy-silicane alkane, four (methoxy ethoxy) silane, four (methoxy propoxy) silane, four (ethoxy ethoxy) silane, four (methoxy ethoxy oxyethyl group) silane, trimethoxy Ethoxysilane, dimethoxy diethoxy silane and related derivatives.
Silane derivative shown in these formulas (I) is well known to those skilled in the art, and they can obtain on market and/or can use standard technology manufacturing well known to those skilled in the art.
The product that silane derivative shown in these formulas (I) and/or said silane derivative produce through hydrolysis and/or condensation is present in the compsn with the content of 1wt% to 35wt%, preferred 5wt% to 20wt%.
As stated, compsn according to the present invention comprises product that the silane derivative shown in the formula (II) and/or said verivate produce through hydrolysis and/or condensation as component (b).
Term " hydrolysate and/or the condensation product of the silane derivative shown in the formula (II) " explanation again; As part of the present invention; Hydrolysis can also take place through forming silanol group in silane derivative (II) at least in part, and to a certain degree crosslinked can take place in the condensation reaction of these silanol groups.
Referring to about residue R
1, R
2, R
3And R
4Above-mentioned information, residue R
5Be preferably alkyl, acyl group, alkylidene group acyl group, naphthenic base, aryl or alkylidene aryl.
The organic residue R that preferably comprises epoxy group(ing)
6Have 2 to 14 carbon atoms.
Residue R
6In epoxy group(ing) preferably exist with the form of glycidoxy, its preferably via following group bonding to Siliciumatom: C
1-10Alkylidene group, preferred C
1-4Alkylidene group such as ethylidene, propylidene or butylidene, arylidene such as phenylene or alkylidene group ether.
Preferred residue R
6Have following chemical formula (III):
Wherein,
R
8Be hydrogen or C
1-4Alkyl is preferably hydrogen, and
R
9For without substituted or through substituted C
1-10Alkylidene group is preferably without substituted or through substituted C
1-4-alkylidene group.
As stated, alkylidene group be understood that divalent alkyl (for example-CH
2-;-CH
2-CH
2-etc.).
Referring to above-mentioned about residue R
1, R
2, R
3And R
4Information, residue R
7Be preferably alkyl, naphthenic base, aryl or alkylidene aryl.
Silane derivative shown in the preferred formula (II) comprises the 3-epoxy third oxygen methyltrimethoxy silane, 3-epoxypropoxy ortho-siliformic acid, 3-epoxypropoxy dimethyl hydroxyl silane, 3-epoxypropoxy dimethylethoxysilane, 3 epoxypropoxy methyldiethoxysilane, 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy triethoxyl silane, 3-epoxypropoxy dimethoxy-methyl silane, 3-epoxypropoxy diethoxymethyl silane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane and related derivatives.
Silane derivative shown in these formulas (II) is well known to those skilled in the art, and they can obtain on market and/or can use standard technology manufacturing well known to those skilled in the art.
The hydrolysate of silane derivative shown in the preferred formula (II) and/or said silane derivative (II) and/or condensation product are present in the compsn with the content of 1wt% to 35wt%, preferred 5wt% to 20wt%.
The weight ratio of silane derivative (I) or its hydrolysate and/or condensation product and silane derivative (II) can change in the scope of broad in theory.
The weight ratio of preferred silane verivate (I) and/or its hydrolysate and/or condensation product and silane derivative (II) and/or its hydrolysate and/or condensation product 95/5 to the scope more than 5/95; Further preferred in 70/30 to 30/70 scope, further preferred in 60/40 to 40/60 scope.
As stated, compsn according to the present invention comprises colloidal inorganic oxide, fluorochemical or oxyfluoride or their mixture as component (c).
Colloidal inorganic oxide, fluorochemical or oxyfluoride are through improving scratch resistance in the network that is attached to existence.In addition, through selecting suitable oxide compound, fluorochemical or oxyfluoride, the specific refractory power of coating can be adjusted to the specific refractory power of base material.
In preferred embodiment, inorganic oxide is selected from SiO
2, TiO
2, ZrO
2, SnO
2, Sb
2O
3, Al
2O
3, AlO (OH) or through blended oxide compound or their mixture or nucleocapsid structure.As for fluorochemical, for example, MgF
2Can be used as pure component or form nucleocapsid structure with one of above-mentioned oxide compound.
The median size of inorganic component should preferably be selected with the mode that does not influence the coating transparency.In preferred embodiment, the colloidal inorganic component has 2nm to 150nm, the more preferably median size of 2nm to 70nm.Median size is measured through dynamic light scattering.
Gross weight with compsn is a benchmark, and preferred colloidal inorganic component is with 1wt% to 40wt%, more preferably the content with 5wt% to 25wt% exists.
As stated, compsn according to the present invention comprise cyclic aliphatic with at least two epoxy group(ing) or aromatics epoxy compounds as component (d).
For example, this epoxy compounds also can be the prepolymer with two above epoxy functional degree.
Therefore, within the scope of the invention, the epoxy compounds of component (d) must have the annular group that is cyclic aliphatic or aromatic units form.
As further described below, to compare with the epoxy compounds of acyclic family, the use of the epoxy compounds of cyclic aliphatic or aromatics causes between scratch resistance, alkali resistance and these performances of bond strength to base material, having improved balance.
Preferred cycloaliphatic compounds be have at least two substituent through substituted hexanaphthene or through the mixture of substituted pentamethylene or these epoxy compoundss or the prepolymer of this compound, wherein said substituting group has at least one epoxy group(ing) separately.
Preferred aromatic substance be have at least two substituent through substituted benzene, through substituted diphenylmethane derivatives or through the mixture of substituted diphenol or these epoxy compoundss or the prepolymer of this compound, wherein said substituting group has at least one epoxy group(ing) separately.
Preferred cyclic aliphatic or aromatic ring oxygen compound have at least two can be identical or different the substituting group that is shown below:
Wherein,
R
8Have aforesaid implication (for example hydrogen or C
1-4Alkyl), and
R
9Has aforesaid implication (C for example
1-10Alkylidene group, preferably C
1-4Alkylidene group),
K is 1-4, is preferably 1-2,
And m is 0 or 1.
For example, resorcinol diglycidyl ether and cyclohexanedimethanodiglycidyl diglycidyl ether or their mixture can be used as cyclic aliphatic or the aromatic ring oxygen compound that preferably has at least two epoxy group(ing).
Gross weight with compsn is a benchmark, and cyclic aliphatic or the aromatic substance that preferably has at least two epoxy group(ing) is with 0.1wt% to 20wt%, preferably the content with 0.5wt% to 10wt% exists.
As stated, compsn according to the present invention comprises solvent as component (e), and this solvent comprises alcohol, ether and/or ester.
If solvent comprises alcohol, this alcohol is preferably selected from monoalky lether or the monoalky lether of alkylene glycol or their mixture of alkanol, cycloalkanol, fragrant and mellow, alkylene glycol, polyoxyethylene enediol so.
Alcohols is selected from C
1-6Alkanol, further preferred C
1-4Alkanol, C
2-4The C of alkylene glycol
1-4Monoalky lether or their mixture.
If solvent comprises ether, this ether is preferably selected from dialkyl ether, ring grease ether, aryl ethers or alkyl aryl ether or their mixture so.
If solvent comprises ester, this ester is preferably selected from alkyl ester, cycloalkyl ester, alkyl aryl, alkylene glycol ester or their mixture so.
With regard to the homogeneity and the optical quality of the coating that makes by said composition,, be favourable to these performances so if solvent comprises two kinds of alcohol, ether or esters with different boiling.
It is second alcohol, ether or the ester of S2 that preferred solvent comprises first alcohol, ether or ester and the boiling point that boiling point is S1, and its mid-boiling point S1 and boiling point S2 can change by following formula:
S1/S2≥1.2
Or
S1/S2≤0.8。
Preferred solvent comprises C
1-4Alkanol is as first alcohol, and the monoalky lether of alkylene glycol, preferred C
2-4The C of alkylene glycol
1-4Monoalky lether is as second alcohol.
Preferred first alcohol is 5 to 0.01 with the weight ratio of second alcohol, further is preferably 2 to 0.2.
Preferred composition also comprises water.In preferred embodiment, be benchmark with the gross weight of compsn, water exists with the content of 2-15wt%.
Preferably also comprise the catalyzer that is used for epoxide polymerization according to compsn of the present invention.
Within the scope of the invention, can use the catalyzer that is used for the photopolymerisable catalyzer of epoxy compounds and is used for the epoxy compounds thermopolymerization.These two kinds of catalyzer groups are well known to those skilled in the art basically.
In preferred embodiment, compsn comprises the catalyzer that is used for the epoxy compounds thermopolymerization, is not used for the photopolymerisable catalyzer of epoxy compounds but do not comprise.
As for the catalyzer that is used for the epoxy compounds thermopolymerization, can use the compound that is used for this purpose well-known to those skilled in the art.
Preferred catalyst comprises Lewis acid (Lewis acid).
For example, be described below for being used for the appropriate catalyst of epoxy compounds thermopolymerization:
An alkali metal salt, an alkali metal salt, fluoride salt and the organo-tin compound of metal acetylacetonates, diamide, imidazoles, amine and ammonium salt, organic sulfonic acid and their amine salt, carboxylic acid and metal alkoxide and their mixture.
Gross weight with compsn is a benchmark, and preferred catalyst exists with the content of 0.01wt% to 5wt%, preferred 0.1wt% to 3wt%.
As for other optional components in the compsn, can relate to tensio-active agent (for example helping film to form), uv-absorbing agent (UV-absorbers), dyestuff and/or stablizer.
According to a further aspect in the invention, a kind of method that is used for coated substrate is provided, it comprises:
-provide aforesaid according to compsn of the present invention,
-compsn is coated on the base material, and
-the processing base material is used for solidified coating under 75 ℃ to 150 ℃ temperature.
With regard to the preferred properties of compsn, can be with reference to above-mentioned explanation.
With regard to coating processes,, will be favourable so if the silane of formula (I) and/or formula (II) has had to a certain degree crosslinked when being coated to base material.For example, the precondensation of qualification can through type (I) and/or the hydrolysis of silane under water or moisture organic acid or mineral acid catalysis of formula (II) realize.
The method that can know by one of skill in the art is coated to compsn on the base material.
For example, can use immersion coating, rotation coating, spraying, gravity flow coating and gap nozzle to apply in this article.
Adopt immersion coating, also can be applied on the substrate surface with more complicated geometry according to compsn of the present invention.
Within the scope of the invention, can use a large amount of different base materials.For example, plastic basis material or even glass baseplate can use according to compsn of the present invention and apply.
For example, the suitable plastic base material can be one or more in the following plastics: polycarbonate, gather (methyl) methyl acrylate, polyurethane(s), polymeric amide, gather diethylene glycol diene propylene carbonate (CR39), polythiourethane such as MR-6, MR-7, MR-8, MR-10, MR-174.
With regard to base material to be coated, those base materials that are used for optical field are preferred.
Concerning base material, preferably be used for plasticity glasses lens or reading lens as lens.
Preferred substrates 75 ℃ to 150 ℃, more preferably at 90 ℃ to 130 ℃ temperature place by thermal treatment.
According to a further aspect in the invention, a kind of goods are provided, it comprises:
-base material, and
-coating on substrate surface, wherein, coating can through or obtain through aforesaid method.
With regard to base material and wait to be applied on the base material and be crosslinked performance subsequently with the compsn that obtains coating, can be with reference to above-mentioned explanation.
According to a further aspect in the invention, the present invention relates to above-mentioned purposes according to compsn coated substrate of the present invention.
Embodiment
Chemical
IPA-ST:SiO
2Nano-solution, Nissan Chemicals manufactured, Houston
The glidant of FC4430:3M manufactured
Other chemical and solvent: Aldrich manufactured
Testing method
The alkali resistance test:
Locate at 50 ℃, through the glass (2.0 dioptrys (dioptres)) that applies in basic solvent (pH＞14) by supersound process 180 seconds.In same point, the bed thickness before and after optical detecting is handled.Hard formation thickness typically is 2.5 μ m.Use degraded layer (layer degradation) to measure alkali resistance then, wherein degraded layer is few more, and alkali resistance is good more.
Measure Bayer (Bayer) test value with COLTS Bayer test set and suitable method, be used to assess scratch resistance.
Via drawing lattice tests (a lattice cutting test) assessment tack coat.
Made and compsn to be tested
Embodiment 1
36 parts resorcinol diglycidyl ethers are dissolved in 162 parts the 1-methoxyl group-2-propyl alcohol of 2-propyl alcohol and 264 parts.In solution, add 186 parts 3-glycidoxy-propyltrimethoxy silane, 150 parts tetraethoxysilane, 240 parts IPA-ST and 126 parts water then, and at room temperature stirred 24 hours.After this add 7.2 parts aluminium acetylacetonate, 25.2 parts 1M ammonium perchlorate soln and 3.6 parts FC4430, further stirred the mixture 3 hours.The solution that makes filters and before coating, is stored in the refrigerator via the strainer of 5 μ m.
Embodiment 2
36 parts 1,4 cyclohexane dimethanol diglycidylethers are dissolved in 162 parts the 1-methoxyl group-2-propyl alcohol of 2-propyl alcohol and 264 parts.Add 186 parts 3-glycidoxy-propyltrimethoxy silane, 150 parts tetraethoxysilane, 240 parts IPA-ST and 126 parts water then, and at room temperature stirred 24 hours.After this add 7.2 parts aluminium acetylacetonate, 25.2 parts 1M ammonium perchlorate soln and 3.6 parts FC4430, further mixture was stirred 3 hours.The solution that makes filters and before coating, is stored in the refrigerator via the strainer of 5 μ m.
Reference examples 1
36 parts trihydroxymethylpropanyltri diglycidyl ethers are dissolved in 162 parts the 1-methoxyl group-2-propyl alcohol of 2-propyl alcohol and 264 parts.Add 186 parts 3-glycidoxy-propyltrimethoxy silane, 150 parts tetraethoxysilane, 240 parts IPA-ST and 126 parts water then, and at room temperature stirred 24 hours.After this add 7.2 parts aluminium acetylacetonate, 25.2 parts 1M ammonium perchlorate soln and 3.6 parts FC4430, further mixture was stirred 3 hours.The solution that makes filters and before coating, is stored in the refrigerator via the strainer of 5 μ m.
Reference examples 2
36 parts tetramethylolmethanes, four glycidyl ethers are dissolved in 162 parts the 1-methoxyl group-2-propyl alcohol of 2-propyl alcohol and 264 parts.In solution, add 186 parts 3-glycidoxy-propyltrimethoxy silane, 150 parts tetraethoxysilane, 240 parts IPA-ST and 126 parts water then, and at room temperature stirred 24 hours.After this add 7.2 parts aluminium acetylacetonate, 25.2 parts 1M ammonium perchlorate soln and 3.6 parts FC4430, further mixture was stirred 3 hours.The solution that makes filters and before coating, is stored in the refrigerator via the strainer of 5 μ m.
Reference examples 3
186 parts 3-glycidoxy-propyltrimethoxy silanes, 186 parts the IPA-ST of tetraethoxysilane and 240 parts are blended in 162 parts 2-propyl alcohol, 264 parts the water of 1-methoxyl group-2-propyl alcohol and 126 parts, and at room temperature stirred 24 hours.After this add 7.2 parts aluminium acetylacetonate, 25.2 parts 1M ammonium perchlorate soln and 3.6 parts FC4430, further mixture was stirred 3 hours.The solution that makes filters and before coating, is stored in the refrigerator via the strainer of 5 μ m.
Before carrying out immersion coating and in 95 ℃ stove after the cured coating film 4 hours with the alkali lye developing technique, the activation test base material.
Alkali resistance (degree via degraded layer is confirmed) and scratch resistance (Bayer test) for the coating that obtains with these compsns are tested.The result who obtains is as shown in table 1.
Table 1: layer test result
The result shows, uses compsn according to the present invention to obtain to have the coating of higher alkali resistance and fine scratch resistance.
By following embodiment, test forms and cohesiveness according to the crackle of coating of the present invention on different substrate materials.
Embodiment 3
36 parts resorcinol diglycidyl ethers are dissolved in 160 parts the 1-methoxyl group-2-propyl alcohol of 2-propyl alcohol and 265 parts.In solution, add 240 parts 3-glycidoxy-propyltrimethoxy silane, 122 parts tetraethoxysilane, 216 parts IPA-ST and 126 parts water then, and at room temperature stirred 24 hours.After this add 6 parts of aluminium acetylacetonates, 25.2 parts 1M ammonium perchlorate soln and 3.6 parts FC4430, further mixture was stirred 3 hours.The solution that makes filters via 5 μ m strainers and before coating, is stored in the refrigerator.
Embodiment 4
69 parts resorcinol diglycidyl ethers are dissolved in 160 parts the 1-methoxyl group-2-propyl alcohol of 2-propyl alcohol and 265 parts.In solution, add 227 parts 3-glycidoxy-propyltrimethoxy silane, 102 parts tetraethoxysilane, 216 parts IPA-ST and 126 parts water then, and at room temperature stirred 24 hours.After this add 6 parts of aluminium acetylacetonates, 25.2 parts 1M ammonium perchlorate soln and 3.6 parts FC4430, further mixture was stirred 3 hours.The solution that makes filters via 5 μ m strainers and before coating, is stored in the refrigerator.
Initial adhesion property and resistance to cracking to the coating that obtained by these compsns are tested.The result who obtains is as shown in table 2.
Table 2: cohesiveness and flaw shaped become performance
These embodiment show, use the coating that obtains according to compsn of the present invention to demonstrate extraordinary base material cohesiveness, and have extraordinary alkali resistance (not having degraded layer) and resistance to cracking simultaneously.
Claims (15)
1. compsn that is used to make coating, it comprises
(a) hydrolysate and/or the condensation product of the silane derivative shown in silane derivative shown in the formula (I) and/or the formula (I),
R wherein
1, R
2, R
3And R
4Can be identical or different, they are selected from optionally can substituted alkyl, acyl group, alkylidene group acyl group, naphthenic base, aryl or alkylidene aryl,
(b) hydrolysate and/or the condensation product of the silane derivative shown in silane derivative shown in the formula (II) and/or the formula (II),
R
6R
7 3-nSi(OR
5)
n (II)
Wherein
R
5Be without substituted or through substituted alkyl, acyl group, alkylidene group acyl group, naphthenic base, aryl or alkylidene aryl,
R
6Be the organic residue that comprises epoxy group(ing),
R
7Be without substituted or through substituted alkyl, naphthenic base, aryl or alkylidene aryl,
N is 2 or 3,
(c) colloidal inorganic oxide, fluorochemical or oxyfluoride,
(d) have the cyclic aliphatic or the aromatic ring oxygen compound of at least two epoxy group(ing),
(e) comprise the solvent of alcohol, ether and/or ester.
2. compsn as claimed in claim 1 is characterized in that, the hydrolysate of the silane derivative shown in silane derivative shown in the said formula (I) and/or the formula (I) and/or condensation product are present in the said compsn with the content of 1wt% to 35wt%.
3. according to claim 1 or claim 2 compsn is characterized in that the said residue R in silane derivative shown in the said formula (II)
6Shown in (III):
Wherein
R
8Be hydrogen or C
1-4Alkyl, and
R
9Be C
1-10Alkylidene group.
4. like each described compsn in the aforementioned claim; It is characterized in that the hydrolysate of the silane derivative shown in silane derivative shown in the said formula (II) and/or the formula (II) and/or condensation product are present in the said compsn with the content of 1wt% to 35wt%.
5. like each described compsn in the aforementioned claim; It is characterized in that the weight ratio of the silane derivative shown in the silane derivative shown in the said formula (I) and/or its hydrolysate and/or condensation product and the said formula (II) and/or its hydrolysate and/or condensation product is 95/5 to 5/95.
6. like each described compsn in the aforementioned claim, it is characterized in that said inorganic oxide is selected from SiO
2, TiO
2, ZrO
2, SnO
2, Sb
2O
3, Al
2O
3, AlO (OH) or mixed oxide compound or its mixture or its nucleocapsid structure, and/or said inorganic fluoride be for can randomly be present in the MgF in the nucleocapsid structure with inorganic oxide
2
7. like each described compsn in the aforementioned claim, it is characterized in that based on the gross weight of said compsn, the content of said colloidal inorganic oxide, fluorochemical or oxyfluoride is 1wt% to 25wt%.
8. like each described compsn in the aforementioned claim, it is characterized in that it can be identical or different substituting groups that said cyclic aliphatic or aromatic ring oxygen compound have at least two, said substituting group is shown below:
Wherein,
R
8Be hydrogen or C
1-4Alkyl,
R
9Be without substituted or through substituted C
1-10Alkylidene group is preferably without substituted or through substituted C
1-4Alkylidene group;
K is 1-4; And
M is 0 or 1.
9. each described compsn as in the aforementioned claim is characterized in that based on the gross weight of said compsn, said have the cyclic aliphatic of at least two epoxy group(ing) or the content of aromatic ring oxygen compound is 0.1wt% to 20wt%.
10. like each described compsn in the aforementioned claim, it is characterized in that said solvent comprises alcohol, said alcohol is selected from: C
1-6Alkanol, preferred C
1-4Alkanol, C
2-4The C of alkylene glycol
1-4Monoalky lether, or their mixture.
11. as each described compsn in the aforementioned claim; It is characterized in that; Said solvent comprises the ether that is selected from down group: dialkyl ether, ring grease ether, aryl ethers or alkyl aryl ether, and/or be selected from down the ester of organizing: alkyl ester, cycloalkyl ester, alkyl aryl or alkylene glycol ester.
12. like each described compsn in the aforementioned claim, it is characterized in that it is second alcohol, ether or the ester of S2 that said solvent comprises first alcohol, ether or ester and the boiling point that boiling point is S1, its mid-boiling point S1 and boiling point S2 can change by following formula:
S1/S2≥1.2
Or
S1/S2≤0.8。
13., it is characterized in that said compsn also comprises the catalyzer that is used for the epoxy compounds thermopolymerization like each described compsn in the aforementioned claim.
14. a method that is used for coated substrate, it comprises:
-provide like each described compsn among the claim 1-13,
-said compsn is coated on the base material, and
-the processing base material is used for solidified coating under 75 ℃ to 150 ℃ temperature.
15. goods, it comprises:
-base material, and
-coating on said substrate surface, wherein
Said coating can be passed through or obtain through method as claimed in claim 14.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33187710P | 2010-05-06 | 2010-05-06 | |
| DE102010028661.3 | 2010-05-06 | ||
| US61/331,877 | 2010-05-06 | ||
| DE102010028661A DE102010028661A1 (en) | 2010-05-06 | 2010-05-06 | Composition for the production of a scratch-resistant coating with improved alkali resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102367364A true CN102367364A (en) | 2012-03-07 |
Family
ID=44262960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110124841XA Pending CN102367364A (en) | 2010-05-06 | 2011-05-05 | Compound for producing a scratch-proof coating with improved lye resistance |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20120115991A1 (en) |
| EP (1) | EP2385086A1 (en) |
| CN (1) | CN102367364A (en) |
| DE (1) | DE102010028661A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011083960A1 (en) * | 2011-10-04 | 2013-04-04 | Carl Zeiss Vision International Gmbh | Composition for the production of a coating with high adhesion and scratch resistance |
| US11198795B2 (en) * | 2015-02-17 | 2021-12-14 | The Walman Optical Company | Glycidyl ether based optical coating compositions |
| EP3273292A1 (en) | 2016-07-19 | 2018-01-24 | Carl Zeiss Vision International GmbH | Spectacle glass and method for its production |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4895767A (en) * | 1985-03-22 | 1990-01-23 | Toray Industries, Inc. | Transparent article and process for preparation thereof |
| CN1138345A (en) * | 1993-11-10 | 1996-12-18 | 新材料公共服务公司研究所 | Process for the production of compounds based on silanes containing epoxy groups |
| CN1257531A (en) * | 1997-04-17 | 2000-06-21 | Sdc涂料公司 | Composition for providing an abrasion resistant coating on a substrate |
| US6537672B1 (en) * | 1998-12-11 | 2003-03-25 | Institut Für Neue Materialien Gem. Gmbh | Powder-coated domestic appliances with a top coat based on epoxy silane |
| CN101153964A (en) * | 2006-09-25 | 2008-04-02 | 精工爱普生株式会社 | Method of manufacturing colored lens |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3986997A (en) | 1974-06-25 | 1976-10-19 | Dow Corning Corporation | Pigment-free coating compositions |
| US4355135A (en) | 1981-11-04 | 1982-10-19 | Dow Corning Corporation | Tintable abrasion resistant coatings |
| JP2613436B2 (en) * | 1988-06-10 | 1997-05-28 | 旭光学工業株式会社 | Method of forming antireflection film for plastic lens |
| AU653825B2 (en) | 1991-06-25 | 1994-10-13 | Itoh Optical Industrial Co., Ltd. | Coating composition for optical plastic moldings |
| US20020061407A1 (en) * | 1998-12-29 | 2002-05-23 | Colton James P. | Abrasion resistant coating composition and coated articles |
| WO2005100020A2 (en) * | 2004-04-09 | 2005-10-27 | Vision-Ease Lens | Primer-less abrasion coating for organic glass articles |
| JP5037348B2 (en) * | 2005-09-02 | 2012-09-26 | 新日鐵化学株式会社 | Epoxy resin composition |
| AU2007344107B2 (en) | 2007-01-16 | 2012-12-13 | Agency For Science, Technology And Research | Hardcoat composition |
| US8084133B2 (en) * | 2008-08-06 | 2011-12-27 | Ppg Industries Ohio, Inc | Tintable film-forming compositions having high refractive indices and coated optical articles using same |
-
2010
- 2010-05-06 DE DE102010028661A patent/DE102010028661A1/en not_active Ceased
-
2011
- 2011-05-02 EP EP11164494A patent/EP2385086A1/en not_active Withdrawn
- 2011-05-05 CN CN201110124841XA patent/CN102367364A/en active Pending
- 2011-05-06 US US13/102,408 patent/US20120115991A1/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4895767A (en) * | 1985-03-22 | 1990-01-23 | Toray Industries, Inc. | Transparent article and process for preparation thereof |
| CN1138345A (en) * | 1993-11-10 | 1996-12-18 | 新材料公共服务公司研究所 | Process for the production of compounds based on silanes containing epoxy groups |
| CN1257531A (en) * | 1997-04-17 | 2000-06-21 | Sdc涂料公司 | Composition for providing an abrasion resistant coating on a substrate |
| US6537672B1 (en) * | 1998-12-11 | 2003-03-25 | Institut Für Neue Materialien Gem. Gmbh | Powder-coated domestic appliances with a top coat based on epoxy silane |
| CN101153964A (en) * | 2006-09-25 | 2008-04-02 | 精工爱普生株式会社 | Method of manufacturing colored lens |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102010028661A1 (en) | 2011-11-10 |
| US20120115991A1 (en) | 2012-05-10 |
| EP2385086A1 (en) | 2011-11-09 |
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Application publication date: 20120307 |